Process for preparing a multi-grade lubricating oil and product



Nov. 15, 1960 H. BEUTHER ETAL PROCESS FOR PREPARING A MULTI-GRADELUBRICATING OIL AND PRODUCT Filed Aug. 2, 1957 NAU INVENTORS hama/.oafwas@ u #een u. .ww/ 5 Jose/2H a. ,verm/Ey 2,960,458 PROCESS FORPREPARING A MULTI-GRADE LUBRICATING OIL AND PRODUCT Harold Beuther, PennTownship, Allegheny County, Al-

fr ed M. Henke, Springdale, and Joseph B. McKinley, Pittsburgh, Pa.,assignors to Gulf Research & Development Company, Pittsburgh, Pa., acorporation oi? Delaware Filed Aug. 2, 1957, Ser. No. 676,039 11 Claims.(Cl. 20S-19) This invention relates to improved procedure for prepartingmulti-grade or multi-viscosity grade lubricating oils and to improvedmulti-grade lubricating oil products.

It has been known to improve lubricating oils by hydrogen treatment, seefor instance U.S. Patents 2,554,282 and 2,787,582. However, suchprocedures have not heretofore been employed to prepare multi-gradelubricating oils. It has furthermore been known to prepare multigradelubricating oils by adding V.I. irnprovers to certain lubricating oilfractions, see for instance Industrial and Engineering Chemistry, volume41, pages 952-959. The addition of these Vl. (viscosity index) improversresults in a product which has the necessary characteristics for amulti-grade oil. However, these products have certain undesirablecharacteristics among which is change in Vl. and viscosity during use.This is due to decomposition of the V.I. improver. Therefore the mixturedoes not have the multi-grade characteristics or lubricity during usethat it had prior to use. This of course is an important defect sincelowering of the V.I. and viscosity greatly modies the value of the oilas a lubricant. As a matter of fact this change during use results in anoil which cannot properly be called a multi-viscosity grade oil.

The invention has for its object to provide procedure for preparingmulti-grade oils by hydrogenation of certain petroleum fractions.Another object is to provide procedure for obtaining multi-gradehydrocarbon lubricants in relatively high yields by hydrogen treatment.A further object is to provide procedure for preparing multigradehydrocarbon lubricants Without utilizing Vl. improving agents. A stillfurther object is to provide improved multi-grade lubricating oils.Other objects will appear hereinafter.

These and other objects of our invention are accomplished by subjectinga deasphalted residuum having a V.I. of between about 75 and 100 and aviscosity at 210 F. of between about 90 and 200 S.U.S. to treatment withhydrogen at a temperature between about 735 and 825 F., at a pressureabove about 2500 p.s,i. and at a space velocity between about 0.4 and1.5. This treatment with hydrogen is carried out in the presence of acatalyst having both aromatic saturation and ring scission activity. Theproduct from the hydrogen treatment is subjected to dewaxing (whennecessary) and is then distilled to yield components which directly, orupon blending with each other, meet the S.A.E. specifications for amultigrade lubricating oil and have a Vl. of 115 or above. Our inventionalso includes the multi-grade lubricating oil product thus produced.Furthermore we have found that the multi-grade lubricating oil productis amenable to conventional lubricating oil additives such asanti-oxidants, detergents and/or corrosion inhibitors and our inventionincludes the multi-grade lubricating oil product into which one or moreof these additives have been incorporated.

In order to obtain high yields of multi-grade oils of the desiredviscosity it is essential to employ a residual type charge stock. Thisis because the conditions necessary to give a multi-grade lube oil aresevere and cause r25,960,458 Patented Nov. 15, 1960 considerable ringscission with formation of lower boiling products. At the same time thisring scission is necessary to obtain the high V.l. required for amulti-grade oil. The starting material may be any residuum obtained byvacuum or like distillation of any petroleum or residual fractionthereof which after deasphalting, preferably with a low boilinghydrocarbon such as propane, propylene or butane, has a V.I. of to 100and a viscosity at 210 F. of to 200 S.U.S. Thus for instance theresiduum may be prepared by vacuum distillation of a Pennsylvania,Mid-Continent, West Texas, Kuwait, etc. crude. We have found thatdeasphalting with agents such as sulfuric acid, phenol, sulfur dioxide,etc. results in removal of components which upon hydrogenation havedesirable properties for a multi-grade oil product and if thesematerials are employed for asphalt removal, the product produced willnot be of as good quality and the yield of multigrade oils will bemarkedly lower. A higher carbon residue will result in undesirableshortening of the life of the catalyst under the relatively severehydrogen treatment conditions employed to produce the multi-grade oil. For this reason we prefer to employ charge stocks having a low carbonresidue such as below about 2 (Conradson). However, higher carbonresidue charge stock may be used if catalyst life is not of greatimportance or a rugged catalyst is used. The utilization of a chargestock having a V.I. of 75 to 100 is essential in obtaining a reasonableyield of a multi-grade oil. 'Ihe high V.I. products necessary formulti-grade lubricating oil, i.e. a V.I. of above about 115, areproduced in good yield only if a charging material of at least about 75V.I. is employed. Excessive ring scission to obtain the Vl. required formultigrade oils will drastically lower yields it a lower than 75 Vl.charge stock is used. A viscosity of between about 90 and 200 S.U.S. at210 F. is necessary so that the multi-grade oil product will have theproper viscosity after the hydrogen treatment.

The reaction conditions specified are necessary to obtain the conversioninto a multi-grade product or to a product containing the multi-gradecomponents. If a temperature much below 735 F. is employed, theconversion to multi-grade oil will not be commercially attractive. Onthe other hand if a temperature much above 825 F. is employed, theconversion into materials having too low a viscosity for multi-grade oilwill be excessive. Within the ranges specified the temperature yandspace velocity can be interchanged to give about the same results. Inother words a low temperature with a lo'w space velocity will give aboutthe same yield rand quality of multi-grade oil as a higher temperatureand higher space velocity. Pressures of below about 2500 p.s.i. do notresult in sutlicient conversion and give an undesirably short catalystlife. Much higher pressures such `as 5000 or even 10,000 may be employedbut are not commercially attractive since they are more costly toproduce and maintain and do not result in much if any improvement inyields or product quality. A pressure of about 3600 to about 4000 p.s.i.is preferred since such pressures result in longer catalyst life and aremost economical. The conditions specied will result in commericallyattractive yields of multi-grade oils and in addition will yieldproducts in about the ratio in which they are consumed. Thus theseconditions will result in a yield of labout one volume of S.A.E. 10W/20multi-grade oi-l to two volumes of S.A.E. 20W/ 30 and/or ZOW/ 40multigrade oil. These are the relative proportions of the market demandfor these multi-grade oils.

The catalyst employed for the hydrogenation must have high activity forsaturation of aromtics and high activity and selectivity for ringscission. Such catalysts are known in the art. For instance they maycomprise a sulfide of any metal of group VI left-hand column of theperiodic the 1S.A.E. yWhen utilizing this method of separatingandVreCQIlbIlsystem mixed Vwith a sulfide of an iron group metal.Specifically the catalyst may be molybdenum sulfide, tungsten sullide orchromium sulfide, etc. mixed fwith a sulfide of iron, vcobalt and/ornickel. A particularly desirable catalyst is a mixture of nickel sulfideand tungsten sulfide. Such a catalyst in la ratio of l to 4 mols ofnickel to 1 of tungsten (determined as metals) has especially highactivity and selectivity. Other examples of satisfactory sulde mixturesare cobalt sulfidetungsten sulfide and nickel sulfide-molybdenumsul-tide mixtures. The catalysts may `be supported or unsupported. A mol`ratio of 1:1 of these mixtures has been found satisfactory.

Pure hydrogen may, of course, be used. However, hydrogen of lower puritysuch as reformer hydrogen Works very well. If an impure hydrogen is usedit is recommended that part of the recycled hydrogen be bled from therecycle stream or that a recycle hydrogen clean-up procedure be used.The hydrogen may be circulated in a ratio of between about 2500 and10,000 s.c.f. per barrel of charge. Higher or lower amounts of hydrogencan be employed. Water should not be present in the hydrogen or othermaterials used in the process since it has a deactivating eect on thecatalyst.

The product from the hydrogenation step Will contain lower boilingreaction products such as gasoline, furnace oil and gases which areunsuitable for multigrade oils. Also if any wax-like materials werepresent in the charge stock they will be present in the product from thehydrogenation. It is necessary to remove these materials from theproduct. The gasoline yand furnace oil can :be removed by stripping ordistillation. Removal of Wax if present is then accomplished by anytreatment conventionally Vused for ydewaxing ordinary lube oils. Thisprocedure is carried out to give fa pour point of between about -5 and-|-5 F. An example of satisfactory dewaxing treatment is dissolving theoil in a solvent such as methyl `ethyl ketone and/ortoluene, propane,etc. and cooling and filtering off the wax. Thereafter the solvent isremoved by distillation. lf a lower pourpoint than that specified aboveis desiredyit can be conveniently obtained by addition of a small amountof any conventional pour point depressant such as Acryloid 618 which is'a polymethacrylate or by addition of polyisobutylenes. It isadvantageous, 'where a charge stock contains wax, to dewax after thehydrogenation since it is easier to remove the wax from the hydrogenatedproduct and a better quality vwax is obtained.

Thehydrogenated and dewaxed (if dewaxing is applied at this stage)product-may be distilled to directly separate fractions which have theproperties of multi-grade oils. Thus the product may be distilled toseparate fractions having the maximum and minimum S.A.E. viscosityrequirements for the multi-grade oil to be produced; for instance for aW/20 multi-grade oil a maximum viscosity at 0 F. of less than 12,000S.U.S. and a viscosity at 210 F. of between 45 and 58 SUS., and foraZOW/ 30 multi-grade oil a maximum viscosity at 0 F. of-less than 48,000S.U.S. and a viscosity at 210 F. of between about 58 and 70 S.U.S. andfor a 20W/40 multi-grade oil a maximum viscosity at 0 F. of less than48,000 S.U.S. and a viscosity at 210 F. of between about 70 and 85S.U.S. These distillates will in each case have a V.I. of above about115 and in most cases above 120 and yashigh as 135 depending upon thereaction conditions and the V.I. of the starting material. Thus thegreater the severity, the higher the V.I. of the product. Also as ageneral rule, the higher the V.I. of the starting material, the higherwill be the V.I. of the product. On the other hand it is satisfactory todistill the hyvdrogenated product to obtain separate fractions forblending to obtain a blended 10W/20 multi-grade oil or a blended 10W/30or 20W/40 multi-grade oil which meet specifications for these`multi-grade oils.

ing portions of fractions of the hydrogenated product, it is probablethat some of the lubricating oil fractions in the 20W/ 30 or 20W/40S.A.E. range Will be added to the lower S.A.E. range oils and vice versato obtain a blended product having the desired characteristics. Theprocedure for blending is Well known to lubricating oil chemists.Regardless of which distillation method is used, light non-lubricatingportions of the product such as gases, gasoline and furnace oil-whichare formed during the hydrogenaton-should be removed or separated fromvthe lube oil fractions. The furnace oil has good burningcharacteristics and the gasoline is a good stock for hydrogen reforming.The distillation should be conducted so as to avoid thermaldecomposition as much as possible. Vacuum and/or distillation with `aninert gas such as steam is employed.

While the process of our invention yields other multigrade oils lwhichcan be separated by distillation, it is of particular value for`preparing the v10W/20, 20W/ 30 and/ or 20W/40 multi-grade oils. Thedemand Vfor these oils is in the approximate ratio of l volume of 10W/20to two volumes of 20W/ 30 or 20W/40 and the operation of our processunder `the conditions specified yields these multi-grade oils in almostexactly this ratio. While the treatment also results in 'conversion ogfthe charge stock into some lighter fractions as explained above,nevertheless these light fractions can Vbe `removed during thedistillation and may be used in other applications where high viscosityis not required. In view of the high yield (S0-.60 percent in mostcases) of lhighquality multi-grade oils, this conversion of `part of-the charge stock into lighter lube fractions does not alter thefavorable economics of our process.

The multi-.grade lubricating oils described herein can be furtherimproved by addition of conventionalror known lubricating oil .additivwThe degree of improvement is equal to and .in many cases greater thanthe mprovement obtained by addition of such conventional additives toother lubricating oils. For instance a 10W/ 20 multi-grade lubricatingoil having a V.I. of 122 prepared by hydrogenation and containing 0.3percent of a conventional pour point inhibitor (Acryloid 618), adetergent comprising a mixture of barium thiophenate and calciumvsulfomrte .(8.0 percent), and 0.9 percent of an antioxidant (zinco,o,dialkyl ydithiophosphate) exhibited unusual properties as comparedwith a conventional lubricating oil having a 1V .1. of 108 to 110 andcontaining the same `amount of additives in addition to 2.0 percent ofAcryloid 966 to produce a Vl. of 125. When these two oils were comparedin the crankcase yof internal combustion engines under identicaloperating conditions, it was found that the octane requirement increase(O.R.I.) of the conventional oil containing the Acryloid V.I. improverwas much greater than that of the hydrogenated oil containing no V.I.improver. This is surprising in view of the `fact that multi-grade oilscontaining Vl. improvers have been recognized `as having a lower O.R`.I.than oils containing no -V.I. improvers. See Some Problems Associated`with the Recommendation and Use of MultiViscosity Oils, Withrow,presented before the Lubricating Committee APl Division of Marketing,Detroit, Michigan, Februray 28,

1956. Our improved multi-grade oils 'are amenable to ,corrosioninhibiting effects.

In the accompanying drawing rwe have illustrated diagnammaticallyapparatus in which your invention may be carried out. Referring to thedrawing, numeral 2 designates a vacuum still into which the crude chargestock such as a topped crude is introduced through conduit 4. Thischarge is fractionated in conventional vfashion to separate gas oil,pressable distillate and unpressable distillate as overhead fractionsand a bottoms fraction for use as a charge stock in the presentinvention. This bottoms fraction is removed from still 2, throughconduit 6 and is introduced into deasphalting equipment 8 where theasphalt is removed in known manner by precipitation in the presence ofpropane which s introduced through conduit 10. Asphalt is removedthrough conduit 12 and the bottoms fraction together with propane isintroduced into still 14 through conduit 16. Here propane is separatedand is recycled through conduit 10. The deasphalte'd bottoms fraction isintroduced into heater `18 through conduit together with hydrogen fromconduit 26 and is then introduced into hydrogen treating reactor 22 viaconduit 24.

In reactor 22 the deasphalted bottoms fraction is hydrogenated inaccordance with the above description. The hydrogen and hydrogenatedproduct are removed from reactor 22 via conduit 28 and introduced intohigh pressure separator 30 where the hydrogen is separated and recycledvia conduit 26. To maintain hydrogen purity, impure hydrogen is bledfrom the system through conduit 31 and make-up hydrogen is added throughconduit 33. The hydrogenated product is removed from high pressureseparator 30 through conduit 32 and is introduced into low pressureseparator 35 where gases are removed and withdrawn lthrough conduit 37.The product is then introduced into still 34 via conduit 39 andsubjected to distillation. Here gasoline and furnace oil are removed asoverhead fractions and a bottoms fraction is removed through conduit 36and introduced into dewaxing unit 38. The hydrogenated lube oil portionof the product is treated in unit 3S in the presence of a dewaxingsolvent such as a mixture of methyl ethyl ketone and toluene at lowtemperature to remove wax which is precipitated and removed throughconduit 40. The dewaxing solvent is introduced into dewaxer 38 throughconduit 42. During dewaxing the wax-like hydrogenation products aresimultaneously removed with any wax products initially present in thecharge stock. 'Ihe product is then removed from de- Waxer 38 throughconduit 44 and is introduced into still 46 where the dewaxing solvent isremoved and recycled through conduit 42. The solvent-free hydrogenationproduct is removed from still 46 through conduit 48 and introduced intovacuum fractionating tower 50 where a light lube oil product is removedoverhead through conduit 52, multi-grade lube oils or multi-grade lubeoil blending stocks are removed as separate cuts or fractions viaconduits 54 and 56. While removal of two such fractions are shown, alarger number of blending or multi-grade fractions can be separated ifdesired.

EXAMPLE l An Ordovician reduced crude having the properties given inTable I was charged to a propane deasphalting unit to yield a productwith the specifications also given in Table I.

Table I Charge Stock Reduced Propane Crude Deasphalted Wt. Percent onCrude 9.1 4. 9 Properties:

Gravity, API 10. 4 23.2

Vis., SUV Seconds 210 F 486 149. 4

Carbon Residue (Conradson) Percent--- 8. 6 lg V Flash, F 615 590 Fire,F. 705 680 Pour, F +40 +90 I, Number (modified Hanns Method) 13.0

The deasphalted product was preheated to about 720 F. and sent to ahydrotreating unit similar to that illustrated in the drawing andcontaining a mixed nickel sulde-tungsten sulfide catalyst in a mol ratioof 4:1. The reaction conditions were 740 F., 0.5 liquid hourly spacevelocity, 5000 s.c.f. of hydrogen per barrel and 3000 p.s.i.g. Theproduct after a high pressure separation of hydrogen was topped atatmospheric pressure and yielded the following percentages of materialsboiling below the specilications for lube oils: (1) gasoline (400 F. endpoint); 7.6% by volume of the charge to the hydrotreater and (2) furnaceoil (670 F. end point); 21.3% by volume of the charge to thehydrotreater. The remaining product was dewaxed by mixing with 4 volumesof a mixture of 60 parts by weight of methyl ethyl ketone mixed with 40parts of toluene followed by cooling to 0 F. to yield 12% by volumecharge to hydrotreater of good quality wax. After removal of thedewaxing solvent the material had a pour point of 0 F. and wasfractionedat 2 mm. pressure with an inert gas being continuously added to thestill pot.

Two blending oils or fractions were separated having the propertiesshown 'in Table II.

Table I1 Yield Percent i I Blending Oils Cut Temp., Vol. Charge F. toHydrotreater u These blending oils were blended to form 10W/20 and 20W/30 multi-grade oils in the proportions shown in Table III. l

Table Ill Composition of Base Oils 10W/20 20W/30 Blending on #1-prcent-- 62. 0 22.1 Blending Oil #2 -do--- 88. 0 77. 9 Yield PercentVol. Charge to Hydrotreater 19.8 37.0

The properties ofthe multi-grade oils so produced and the S.A.E.specification range for such oils are shown in Table IV.

perature of 745 F.; a space velocity of 0.5, a pressure of 3000 p.s.i.g.and a hydrogen recycle rate of 5000 s.c.f. per barrel of charge. Thesame catalyst was employed as in Example I and the product was dewaxedto a pour point of 0 F. and fractionated in the same manner as inExample I to obtain blending oils at the temperaturesY indicated inTable'V.

Table V Yield Percent Blending Oils Out Temp., Vol." Charge l?.Y toHydrotreater #1 725-890v i 18.5 #2 l 890-]- 37.5

The blending oils shown 4in Table V were-blended in the proportionsshown in Table VI to obtain a W/ 20 multi-grade and 'a l20W/40multi-grade oil.

Table VI Composition of Base Oils 10W/20 2q() W/t() Blending oi1#1 75. oBlending Oil #2 25.0 100 Yield Percent Vol. of Gharge'to'Hydrotrcater24. 8 31. 2

The properties of the multi-grade oilsv and the S.A.E. specificationranges for these multi-grade oils are shown in Table VII.

Analysis of typical 10W/'20, 20W/30 and 20W/40 multi-grade lubricatingoil products produced by the herein deseribednreeess .shew .that theyhave the @115 of properties given in Table VIII.

Table VIII Composition: Mol percent A-lkanes 1-3 Non-condensed cycloalkanes 65-78 Condensed cyclo albanes- 2 ring 1 16-19 3 ring 4-7 4 ring2-3 5 ring 1-2 6 ring 0-0.5 Alkyl benzenes 1-2 Alkyl naphthalenes 0-0.3Inspections:

API 30D-33.0 Viscosity, SUV seconds-,-

100 P. 150-580 210211. 45-85 Viscosity index 1115-135 Iodine number1.5-2.2 Mol weight 380-700 Carbon residue V 0.0-0.2

We claim:

1. 'Ilhe method of producing a multi-grade lubricating oil by treatmentwith hydrogen to obtain combined hydrogenation and ring scission whichcomprises in ycombination treating a ,-deasphalted residuum having -aVl. between about 75-1and 100 and a Viscosity at 210 F. of between about90 and 200 S.U.S. with hydrogen at a temperature between .about 735 and825 F.; zat `a pressure above `about 2500 p.s.i., at a space velocitybetween about 0.4 `and 1.5, and in the presence of a catalyst comprisingessentially fa mixture ofthe suldes of a metal of group VI left-handY'column )ofthe peiiodic system and iron group metals, `dewaxing theproduct to a pour point below about 5 F. and subjecting the dewaxedproduct to vacuum distillation to separate components within the maximum`and minimum viscosity limits of the S.A.E. speciiications for `amulti-grade lubricating oil, said components having 1a V.I. of atleast115.

2. The method of producing a multi-grade lubricating oil by treatmentwith hydrogen to obtain combined hydrogenation and ring scission whichcomprises in combination treating a vacuum tower residuum which has beendeasphalted with `a low boiling `hydrocarbon and which afterdeasphalting has a V.I. between about 75 and 100 yand a viscosity at 210F. between Irabout 90 and 200 S.U.S. with hydrogen `at a temperaturebetween about 735 and 825 F., at a pressure 'above about 2500 p.s.i., ata space velocity between about 0.4 and 1.5 'and in the presence of acatalyst comprising essentially la sulde of a metal of group VIl of ltheperiodic'system mixed with a sull-1de of an iron group metal, strippingLand dewaxing the product to a pour point between about `5 and +5 F. andsubjecting the product to vacuum distillation to separate a fractionwithin the maximum and minimum viscosity limits for a member of thegroup consisting of S.A.E. 10W/20, S.A.E. 20W/ 30 and S.A.E. 20W/40multi-grade lubricating oils and having a viscosity index of at least115.

3. The method of producing `a multi-grade lubricating loil by treatmentwith hydrogen to obtain combined hydrogenation and ring scission whichcomprises in combination treating a vacuum tower residuum which has beendeasphalted with a low boiling hydrocarbon and which after deasph-altinglhas a Vl. between yabout 75 and 100 and a viscosity at 210 F. betweenabout 90 and 200 S.U.S. with hydrogen at a temperature between about 735and 825 F., at ya pressure above -about 2500 p.s.i., `at a spacevelocity between about 0.4 land 1.5, and in the presence of Ia catalystAcomprising essentially a suliidel of a metal of group VI of the periodicsystem mixed with a sulfide of an iron group metal, stripping anddewaxing the product to a pour point between about 5 and +5 F.,subjecting the product to vacuum `distillation to separate a pluralityof fractions having a Vl. above about 115 and blending these fractionsto produce a multi-grade oil having the maximum and minimum viscositiesfor S.A.E. 10W/20, S.A.E. 20W/ 30 `and S.A.E. 20W/40 multi-gradelubricating oils in the approximate ratio of one Volume of S.A.E. 10W/20 to two volumes of S.A.E. 10W/30 and 20W/40 multi-grade lubricatingoils.

4. The method of producing a multi-grade lubricating oil by treatmentwith hydrogen to obtain combined hydrogenation and ring scission whichcomprises in combination treating a vacuum tower residuum which hasbeendeasphalted with propane and which after deasphalting has a carbonresidue below about 2.0 percent, a V.I. between about 75 and 100 and aviscosity -at 210 F. of between about and 200 S.U.S. with hydrogen at atemperature between about 735 and 825 F., at a pressure of about3600-4000 p.s.i., at a space velocity between about 0.4 and 1.5 and inthe presence of a catalyst comprising essentially a mixture of nickeland tungsten suliides and subjecting the product from the hydrogentreatment to dewaxing to a pour point below about 5 F. and todistillation to separate fractions within the maximum and minimumviscosity limits for S.A.E. 10W/20, S.A.E. 20W/30 and S.A.E. 20W/40multi-grade lubrieating oils and having viscosity indices of Aat least115.

5. The method of producing `a multi-grade lubricating oil by treatmentwith hydrogen to obtain combined hydrogenation 4and ring scission whichcomprises in combination treating a vacuum tower residuum which hasVbeen deasphalted with propane and which after deasphal/ting has a Vl.between yabout 75 and 100 and a viscosity at 210 F. of between about 90and 200 S.U.S. with hydrogen at a temperature vbetween about 735 and,825

F., at a pressure of Iabout 3600-4000 p.s.i., at a space velocitybetween about 0.4 and 1.5 and in the presence of a catalyst comprisingessentially a mixture of nickel and tungsten suliides, distilling theproduct to remove materials boiling below lube oil fractions, strippingand dewaxing the product to a pour point between about -5 and -\-5 F.,subjecting the product to vacuum distillation to separate fractionshaving a VI. above 115 and blending at least two fractions to obtain ablend having the maximum and minimum viscosities for a member of thegroup consisting of S.A.E. 10W/20, S.A.E. 20W/30 and 20W/40 multi-gradelubricating oils.

6. As a new composition of matter a multi-grade lubricating oil which issubstantially devoid of any added viscosity index improving material andcomprising essentially a mixture of hydrogenated Ihydrocarbons havingthe characteristics of `a multi-grade oil selected from the groupconsisting of S.A.E. 10W/20, S.A.E. 20W/ 30 and S.A.E. 20W/40multi-grade oils, the S.A.E. 10W/20 multi-grade oil having -a Vl. of atleast 115, a viscosity at F. of below about 12,000 S.U.S., a viscosityat 210 F. of between about 45 and 58 S.U.S., a pour point of below about-l- F. `and an iodine number below about 2, and the S.A.E. ZOW/ 30multi-grade oil having a V.I. of at least 115, a viscosity at 0 F. ofbelow about 48,000 S.U.S., a viscosity at 210 F. of between about 58 and70 S.U.S., `a pour point of below about -}5 F., and -an iodine numberbelow about 2 and the S.A.E. 20W/40 multi-grade oil having a Vl. of atleast 115, a viscosity at 0 F. of below about 48,000 S.U.S., -aviscosity at 210 F. of between about 70 and 85 S.U.S., a pour point ofbelow about +5 F. and an iodine number below about 2, said compositionbeing obtained by hydrogenation of a deasphalted residuum anddistillation of the hydrogenated product to separate a member of thegroup consisting of fractions which upon blending yield these S.A.E.multi-grade oils and fractions having the properties of thesemulti-grade oils.

7. As -a new composition of matter a multi-grade lubricating oil whichis substantially devoid of any added viscosity index improving materialand comprising essentially a mixture of hydrogenated hydrocarbons havingthe characteristics of an S.A.E. W/ 20 multi-grade oil, said compositionhaving a V.I. of at least 115, a viscosity at 0 F. of below about 12,000S.U.S., a viscosity at 210 F. of between about 45 and 58 S.U.S., a pourpoint of below about |5 F., an iodine number below about 2 to which hasbeen added at least one lubricating oil additive.

8. As a new composition of matter a multi-grade lubricating oil which issubstantially devoid of any added viscosity index improving material andcomprising essentially a mixture of hydrogenated hydrocarbons having thecharacteristics of an S.A.E. 20W/ 30 multi-grade oil, said compositionhaving a V.I. of at least 115, a viscosity at 0 F. of below about 48,000S.U.S., a viscosity at 210 10 F. of between about 58 and 70 S.U.S., apour point of below about +5 F., an iodine number below about 2 to whichhas been added at least one lubricating oil additive.

9. As a new composition of matter a multi-grade lubricating oil which issubstantially devoid of any added viscosity index improving material andcomprising essentially a mixture of hydrogenated hydrocarbons having thecharacteristics of an S.A.E. 20W/40 multi-grade oil, said compositionhaving a VI. of at least 115, a viscosity at 0 F. of below about 48,000S.U.S., a viscosity at 210 F. of between `about and 85 S.U.S., a pourpoint of below about l-5 F., an iodine number below about 2 to which hasbeen added at least one lubricating oil additive.

10. The method of producing a multi-grade lubricating oil by treatmentwith hydrogen to obtain combined hydrogenation and ring scission whichcomprises in combination treating -a deasphalted residuum having a V.I.between about and 100 and a viscosity of 210 F. of between about and 200S.U.S. with hydrogen at a temperature between about 735 and 825 F., at apressure above about 2500 p.s.i., at a space velocity between about 0.4and 1.5, and in the presence of an unsupported catalyst comprisingessentially a mixture of the suldes of a metal of group VI left-handcolumn of the periodic system and iron group metals, and subjecting theproduct to vacuum distillation to separate components within the maximumand minimum viscosity limits of the S.A.E. speciiications for amulti-grade lubricating oil, said components having a V.I. of at least115,

11. The method of producing a multi-grade lubricating oil by treatmentwith hydrogen to obtain combined hydrogenation and ring scission whichcomprises in combination treating a deasphalted residuum Ih-aving a V.I.between about 75 and 100 and a viscosity at 210 F. of between about 90and 200 S.U.S. with hydrogen at a temperature between about 735' and 825F., at a pressure about about 2500 p.s.i., at a space velocity betweenabout O.4 and 1.5, and in the presence of a catalyst comprisingessentially a mixture of the suldes of a metal of group VI left-handcolumn of the periodic system and iron group metals composited with -acatalyst support, and subjecting the product to vacuum distillation toseparate components within the maximum and minimum viscosity limits fora multi-grade lubricating oil, said components having a V.I. of at least115.

References Cited in the file of this patent UNITED STATES PATENTS2,554,282 Voorhies May 22, 1951 2,779,711 Goretta Jan. 29, 19572,787,582 Watkins Apr. 2, 1957 2,904,505 Cole Sept. 15, 1959

6. AS A NEW COMPOSITION OF MATTER A MULTI-GRADE LUBRICATING OIL WHICH ISSUBSTANTIALLY DEVOID OF ANY ADDED VISCOSITY INDEX IMPROVING MATERIAL ANDCOMPRISING ESSENTIALLY A MIXTURE OF HYDROGENATED HYDROCARBONS HAVING THECHARACTERISTICS OF A MULTI-GRADE OIL SELECTED FROM THE GROUP CONSISTINGOF S.A.E. 10W/20, S.A.E. 20W/30 AND S.A.E. 20W/40 MULTI-GRADE OILS, THES.A.E. 10W/20 MULTI,GRADE OIL HAVING A V.I. OF AT LEAST 115, A VISCOSITYAT AT 0% F. OF BELOW ABOUT 12,000 S.U.S., A POUR POINT 210*F OF BETWEENABOUT 45 AND 58 S.U.S., A POUR POINT OF BELOW ABOUT +5*F. AND AN IODINENUMBER BELOW ABOUT 2, AND THE S.A.E. 20W/30 MULTI-GRADE OIL HAVING AV.I. OF AT LEAST 115, A VISCOSITY AT 0*F. OF BELOW ABOUT 48,000 S.U.S.,A VISCOSITY AT 210*F. OF BETWEEN ABOUT 58 AND 70 S.U.S., A POUR POINT OFBELOW ABOUT +5*F., AND AN IODINE NUMBER BELOW ABOUT 2 AND THE S.A.E.20W/40 MULTI-GRADE OIL HAVING A V.I. OF AT LEAST 115, A VISCOSITY AT210*F. OF BETWEEN ABOUT 70 AND 85 S.U.S., VISCOSITY AT 210*F. OF BETWEENABOUT 70 AND 85 S.U.S., A POUR POINT OF BELOW ABOUT +5*F. AND AN IODINENUMBER BELOW ABOUT 2, SAID COMPOSITION BEING OBTAINED BY HYDROGENATIONOF A DEASPHALTED RESIDUUM AND DISTILLATION OF THE HYDROGENATED PRODUCTTO SEPARATE A MEMBER OF THE GROUP CONSISTING OF FRACTIONS WHICH UPONBLENDING YIELD THESE S.A.E. MULTI-GRADE OILS AND FRACTIONS BLENDING THEPROPERTIES OF THESE MULTI-GRADE OILS.